EP4110865A1 - Alkylverbrückte thermische stabilisatoren auf zinnbasis für halogenierte harze sowie synthese und verwendungen davon - Google Patents
Alkylverbrückte thermische stabilisatoren auf zinnbasis für halogenierte harze sowie synthese und verwendungen davonInfo
- Publication number
- EP4110865A1 EP4110865A1 EP21761815.6A EP21761815A EP4110865A1 EP 4110865 A1 EP4110865 A1 EP 4110865A1 EP 21761815 A EP21761815 A EP 21761815A EP 4110865 A1 EP4110865 A1 EP 4110865A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- stabilizer
- alkyl
- tin
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003017 thermal stabilizer Substances 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title description 10
- 238000003786 synthesis reaction Methods 0.000 title description 10
- 229920005989 resin Polymers 0.000 title description 2
- 239000011347 resin Substances 0.000 title description 2
- 239000003381 stabilizer Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 17
- 239000004800 polyvinyl chloride Substances 0.000 claims description 16
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000004801 Chlorinated PVC Substances 0.000 claims description 5
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims 12
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- -1 but not limited to Substances 0.000 description 10
- 241000894007 species Species 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical group CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 2
- PYPQFOINVKFSJD-UHFFFAOYSA-N S[S] Chemical compound S[S] PYPQFOINVKFSJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000006077 pvc stabilizer Substances 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
Definitions
- the present invention relates to stabilizer composition for halogen-containing polymer. More particularly, the present invention relates to thermal stabilizers for halogen-containing stabilizers, for example polyvinyl chloride or PVC.
- PVC specifically is a thermally unstable polymer at traditional processing temperatures and many stabilizer systems have been developed that attempt to address its inherent thermal instability. These multiple approaches include organic, mixed metal and tin-based stabilizers.
- PVC and related polymers are also blended and compounded with a variety of other ingredients including, but not limited to, pigments, fillers, lubricants, process aids and impact modifiers. These mixtures are heated during blending and processing by methods including extrusion and injection molding which can lead to the release of volatile materials. These materials may lead to unpleasant odors and/or have potential health effects on exposed workers and part of these volatiles during compounding and processing can be traced to the stabilizing system.
- Examples of technologies to lower volatile materials include polymer plasticizers, post stripping the stabilizer to remove the volatile material, post adding an alkyl tin oxide to react with residual Mercaptoester, and, using higher molecular weight esters.
- tin-based stabilizers for PVC include the use of ‘bridging sulfur’.
- the bridging sulfur moieties are reactive and form part of the stabilizing action of the stabilizer containing such groups.
- these sulfur bridging groups are transitory in nature and do not effectively increase the molecular weight of such stabilizers and therefore have do not lower the volatility of such materials with respect to their non-sulfur bridged counterparts.
- the alkyl-bridged stabilizers of the present invention overcomes these problems.
- the present invention is a stabilizer composition for halogen-containing polymer. It has recently been found that tin-based thermal stabilizers with a bridging alkyl group between two tin centers are effective stabilizers while having effectively double the molecular weight of the corresponding non-alkyl bridged stabilizer.
- the alkyl bridged stabilizers have much lower volatility which leads to greater retention of the stabilizer in the finished article. It is expected that other bridging groups, including non-carbon-based bridging groups, would yield similar results.
- alkyl bridged materials described herein are based on tin-alkyl bonds which are not active in the stabilization process and are effective in increasing molecular weight of the stabilizing system. This approach is not limited to monomeric species containing 2 tin sites with a single bridging group and species with multiple tin sites, greater than 2, based on single or multiple tin-terminated alkyl-based bridges should also behave in similar manner.
- Figure 1 is a chart showing thermogravimetric analysis in °C
- FIG. 2 is a chart showing TGA of Monobutyltin Trichloride (MT).
- FIG. 3 is a chart showing TGA of Octyl Ditin Hexachloride (BT).
- Figure 4 shows preferred embodiments of the stabilizers of the present invention.
- Figure 5 shows other possible bridging groups.
- the present invention is a stabilizer composition for halogen-containing polymer. It has recently been found that tin-based thermal stabilizers with a bridging alkyl group between two tin centers are effective stabilizers while having effectively double the molecular weight of the corresponding non-alkyl bridged stabilizer. The alkyl bridged stabilizers have much lower volatility which leads to greater retention of the stabilizer in the finished article.
- BT can be viewed as an effective dimer of the MT species, which would result from the use of a traditional non-bridged tin stabilizers of the sort monobutyltin tris(EHMA). Both of the chlorides in Fig. 1 would be created as the ultimate stabilization product by displacement of the reactive ligands of their respective starting thermal stabilizers. In addition to lower weight loss during processing, it is expected that bridging species will also be less susceptible to extraction during their in-use lifetimes.
- Test Conditions The PVC compound was blended following standard additive addition order and temperature. The color stability of each compound was evaluated using a Brabender running operating at 190 degrees Celsius / 60 rpm with samples taken in 2- minute intervals. The colors of each chip were measured relative to a standard white tile and “L Values” and “b Values” reported in the tables 2 and 3, respectively, below.
- ChSn-CxHk,-SnCh Olethyl Ditin Hexachloride
- Test Conditions The PVC compound was blended following standard additive addition order and temperature. The color stability of each compound was evaluated using a Brabender running operating at 190 degrees Celsius / 60 rpm with samples taken in 2- minute intervals. The colors of each chip were measured relative to a standard white tile and “L Values” and “b Values” reported in the tables 2 and 3, respectively, below.
- Samples 1 and 2 are non-alkyl bridged and alkyl-bridged species based on octyltin centers and EHMA as ligand. At equivalent tin the alkyl-bridged species provides effectively equivalent stabilizing performance versus its non-bridged counterpart as judged by the similarity of the color development as outlined in Tables 2 and 3.
- Samples 3 and 4 are non-alkyl bridged and alkyl-bridged species based on octyltin centers and RE as ligand. At equivalent tin the alkyl-bridged species provides effectively equivalent stabilizing performance versus its non-bridged counterpart as judged by the similarity of the color development as outlined in Tables 2 and 3.
- the stabilizer composition of the present invention for halogen-containing polymers preferably comprises at least two tin-based centers having a bridging alkyl group between the tin-based centers. This formula can have multiple tin-based centers and corresponding multiple bridging alkyl groups.
- the stabilizer may be of one of the following types:
- L is preferably a traditional ligand, such as esters of thioglycobc acid, 2-ME esters of C12-C18 fatty acids, carboxylates, maleates, sulfides, 2-ME, mercaptans, or any blends thereof.
- X and Y are preferably tin-terminated alkyl-based bridging groups. X and or Y can be linear or branched, saturated or unsaturated, with or without heteroatoms, and/or with or without heterocycles.
- the alkyl bridge is preferably Cl to C80.
- the stabilizer composition comprises at least three repeating units of -[SnL 2 -X-] n, where X is a tin-terminated alkyl-based bridging group and L is a traditional ligand.
- X may be linear or branched, saturated or unsaturated, with or without heteroatoms, and/or with or without heterocycles.
- the alkyl bridge is Cl to C80.
- L is an ester of thioglycobc acid, a 2-ME ester of C12-C 18 fatty acids, a carboxylate, a maleate, a sulfide, 2-ME, a mercaptan, or any combination of two or more of an ester of thioglycobc acid, a 2-ME ester of C 12-C 18 fatty acids, a carboxylate, a maleate, a sulfide, 2-ME, or a mercaptan.
- the present invention also includes the resulting PVC, CPVC, or a blend of PVC and CPVC that contains the novel stabilizer described above.
- the resulting composition contains at least 0.5% by weight stabilizer.
- silicones silicones
- silanes silanes
- silazanes silazanes
- carbosilances silphenylenes
- the present invention also includes a method of preparing the novel alkyl-bridged stabilizer.
- the present invention also includes a method of preparing PVC, CPVC, or blends thereof containing the novel alkyl-bridged stabilizer.
- these compositions are prepared according to Synthesis Route A or B described above.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202062980834P | 2020-02-24 | 2020-02-24 | |
| PCT/US2021/019449 WO2021173697A1 (en) | 2020-02-24 | 2021-02-24 | Alkyl-bridged tin-based thermal stabilizers for halogenated resins and synthesis and uses therof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP4110865A1 true EP4110865A1 (de) | 2023-01-04 |
| EP4110865A4 EP4110865A4 (de) | 2024-04-10 |
Family
ID=77365854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21761815.6A Pending EP4110865A4 (de) | 2020-02-24 | 2021-02-24 | Alkylverbrückte thermische stabilisatoren auf zinnbasis für halogenierte harze sowie synthese und verwendungen davon |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20210261754A1 (de) |
| EP (1) | EP4110865A4 (de) |
| JP (1) | JP2023515281A (de) |
| KR (1) | KR20220149695A (de) |
| CN (1) | CN115836109A (de) |
| BR (1) | BR112022016880A2 (de) |
| CA (1) | CA3163442A1 (de) |
| CL (1) | CL2022002305A1 (de) |
| CO (1) | CO2022013699A2 (de) |
| EC (1) | ECSP22074644A (de) |
| GB (1) | GB2608041B (de) |
| MX (1) | MX2022010409A (de) |
| PE (1) | PE20221684A1 (de) |
| WO (1) | WO2021173697A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350090B (zh) * | 2022-01-20 | 2023-07-14 | 济南新材料产业技术研究院 | 一种耐高温型高分子合金桥架及其制备方法和应用 |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE618626A (de) * | 1961-06-08 | 1900-01-01 | ||
| US3398114A (en) * | 1964-01-10 | 1968-08-20 | Argus Chem | Light and heat stability of polyvinyl chloride resins |
| US3933750A (en) * | 1973-05-10 | 1976-01-20 | Albright & Wilson Limited | Novel stabilized polymer compositions |
| US3979359A (en) * | 1974-11-15 | 1976-09-07 | Cincinnati Milacron Chemicals, Inc. | Carbofunctional sulfur and carboxylate bridged tin compounds |
| US6919392B1 (en) * | 1978-08-29 | 2005-07-19 | Arkema Inc. | Stabilization of vinyl halide polymers |
| US4314934A (en) * | 1981-02-26 | 1982-02-09 | Carstab Corporation | Organohalide polymers stabilized with an organotin compound and an ortho mercapto phenol compound |
| US4386189A (en) * | 1981-05-05 | 1983-05-31 | Delaware City Plastics Corporation | Process for the post-chlorination of vinyl chloride polymers |
| EP0149696A1 (de) * | 1984-01-23 | 1985-07-31 | The Dow Chemical Company | Polymerisierbare UV-Stabilisatoren von Isocyanat-Alkyl-Ester von ungesättigten Carbonsäuren |
| US5100946A (en) * | 1990-12-27 | 1992-03-31 | Atochem North America, Inc. | Stabilized halogen containing polymer compositions |
| CA2284498A1 (en) * | 1998-10-13 | 2000-04-13 | Michael E. Skladany | A pleasantly fragrant process for stabilizing halogen-containing polymers |
| US6258880B1 (en) * | 1998-11-25 | 2001-07-10 | Morton International, Inc. | Stabilizers for improved weatherability of clear polyvinyl chloride compositions |
| US7794494B2 (en) * | 2002-10-11 | 2010-09-14 | Boston Scientific Scimed, Inc. | Implantable medical devices |
| US20140336316A1 (en) * | 2011-11-30 | 2014-11-13 | Rohm And Haas Company | Stabilized polymer compositions |
| KR102307977B1 (ko) * | 2018-07-31 | 2021-09-30 | 삼성에스디아이 주식회사 | 반도체 레지스트용 조성물 및 이를 이용한 패턴 형성 방법 |
| CN109988382B (zh) * | 2019-04-04 | 2021-02-09 | 中国人民解放军61699部队 | 一种pvc热稳定剂组合物、制备方法及其使用方法 |
-
2021
- 2021-02-24 JP JP2022576331A patent/JP2023515281A/ja active Pending
- 2021-02-24 US US17/184,298 patent/US20210261754A1/en active Pending
- 2021-02-24 EP EP21761815.6A patent/EP4110865A4/de active Pending
- 2021-02-24 WO PCT/US2021/019449 patent/WO2021173697A1/en active Application Filing
- 2021-02-24 GB GB2212630.4A patent/GB2608041B/en active Active
- 2021-02-24 KR KR1020227032859A patent/KR20220149695A/ko unknown
- 2021-02-24 BR BR112022016880A patent/BR112022016880A2/pt unknown
- 2021-02-24 CA CA3163442A patent/CA3163442A1/en active Pending
- 2021-02-24 MX MX2022010409A patent/MX2022010409A/es unknown
- 2021-02-24 CN CN202180016380.6A patent/CN115836109A/zh active Pending
- 2021-02-24 PE PE2022001742A patent/PE20221684A1/es unknown
-
2022
- 2022-08-23 CL CL2022002305A patent/CL2022002305A1/es unknown
- 2022-09-23 CO CONC2022/0013699A patent/CO2022013699A2/es unknown
- 2022-09-23 EC ECSENADI202274644A patent/ECSP22074644A/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021173697A1 (en) | 2021-09-02 |
| GB2608041B (en) | 2024-05-15 |
| GB2608041A (en) | 2022-12-21 |
| KR20220149695A (ko) | 2022-11-08 |
| CO2022013699A2 (es) | 2022-10-11 |
| WO2021173697A4 (en) | 2021-10-14 |
| GB202212630D0 (en) | 2022-10-12 |
| CL2022002305A1 (es) | 2023-04-21 |
| PE20221684A1 (es) | 2022-11-02 |
| ECSP22074644A (es) | 2022-10-31 |
| BR112022016880A2 (pt) | 2022-10-18 |
| JP2023515281A (ja) | 2023-04-12 |
| EP4110865A4 (de) | 2024-04-10 |
| CN115836109A (zh) | 2023-03-21 |
| US20210261754A1 (en) | 2021-08-26 |
| MX2022010409A (es) | 2022-09-07 |
| CA3163442A1 (en) | 2021-09-02 |
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